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EP3507321B1 - Procede destine a la fabrication de matieres synthetiques de polyisocyanurate en catalyse par phosphine - Google Patents

Procede destine a la fabrication de matieres synthetiques de polyisocyanurate en catalyse par phosphine Download PDF

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Publication number
EP3507321B1
EP3507321B1 EP17761849.3A EP17761849A EP3507321B1 EP 3507321 B1 EP3507321 B1 EP 3507321B1 EP 17761849 A EP17761849 A EP 17761849A EP 3507321 B1 EP3507321 B1 EP 3507321B1
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EP
European Patent Office
Prior art keywords
polyisocyanate composition
weight
process according
polyisocyanate
carbon atoms
Prior art date
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EP17761849.3A
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German (de)
English (en)
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EP3507321A1 (fr
Inventor
Dieter Mager
Hans-Josef Laas
Mathias Matner
Dirk Achten
Heiko Hocke
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Covestro Intellectual Property GmbH and Co KG
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Covestro Intellectual Property GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

  • the invention relates to a process for producing polyisocyanurate plastics, to the polyisocyanurate plastics obtainable by this process, and to coatings, films, semifinished products or mouldings produced therefrom.
  • Polymers with polyisocyanurate structure are known for their good thermal stability and flame resistance.
  • Polyisocyanurate foams based on the aromatic diphenylmethane 4,4'-diisocyanate (MDI) are widely used, for example, because of their very low thermal conductivity, especially as high-performance insulating materials.
  • MDI polyisocyanurates as is commonly known from aromatic polyurethanes, have only low light stability and have a tendency to significant yellowing.
  • European Polymer Journal, vol. 16, 147-148 (1980 ) describes the catalytic trimerization of monomeric 1,6-diisocyanatohexane (HDI) at 40°C to give a clear transparent polyisocyanurate plastic free of isocyanate groups. For this purpose, however, 15% by weight of dibutyltin dimethoxide are required as trimerization catalyst.
  • European Polymer Journal, Vol. 16, 831-833 (1980 ) describes the full trimerization of monomeric HDI to give a polyisocyanurate at a temperature of 140°C using 6% by weight of tributyltin oxide as catalyst.
  • JP 2001-098042 provides polyisocyanurates proceeding from monomeric cycloaliphatic bis(isocyanatomethyl)norbornane (NBDI) having a maximum isocyanate group content of 13% in the end product and prepared using a catalyst system consisting of potassium fluoride and a complexing agent containing ethylene oxide groups.
  • NBDI monomeric cycloaliphatic bis(isocyanatomethyl)norbornane
  • WO 2015/166983 describes the use of polyisocyanurate plastics for encapsulation of LEDs. There are no pointers in this publication to the specific trimerization catalysts used in the process of the present invention and to their low sensitivity to moisture.
  • EP 0 481 318 and DE 10 2004 038784 relate to the manufacture of oligomeric polyisocyanates which are the raw materials of the method of the present invention. They do not disclose the manufacture of polyisocyanurate plastics.
  • the invention provides a process for producing a polyisocyanurate plastic, comprising the following steps:
  • the invention also provides the polyisocyanurate plastics obtainable by this process and the use thereof for production of coatings, films, semifinished products or mouldings. Particular preference is given to using the polyisocyanurate plastic obtainable by the process according to the invention for production of mouldings.
  • the invention described in detail hereinafter is based on the surprising observation that low-monomer oligomeric polyisocyanate compositions, through catalysis with tertiary organic phosphines, even under non-inert conditions, can be trimerized to give blister-free transparent polyisocyanurate plastics that have many advantageous properties and are especially suitable for optical applications and components.
  • blister-free trimerization is possible not only in the presence of air humidity but even in direct contact with liquid water, for example underwater.
  • polyisocyanurate plastic as used herein is a plastic containing polyisocyanurate. It may also consist predominantly or entirely of a polyisocyanurate. Blends composed of polyisocyanurates and other plastics are likewise covered by the term “polyisocyanurate plastic” as used here.
  • plastic when reference is made here to “plastic”, this means a product which is very substantially dimensionally stable at room temperature - in contrast, for example, to gels or liquids.
  • plastic includes all customary classes of plastic, i.e. in particular including thermosets, thermoplastics and elastomers.
  • a "polyisocyanurate” as used here is any molecule having a plurality of isocyanurate structural units, for example at least 10 isocyanurate structural units.
  • a molecule having a single isocyanurate structural unit can be referred to as "isocyanurate”.
  • a “moulding” in the context of this patent application is a body having, in its direction of lowest expansion, a thickness of at least 0.5 mm, preferably at least 1 mm, more preferably at least 2 mm and most preferably at least 5 mm. More particularly, a “moulding” as used here is not a film, coating or membrane.
  • Isocyanurates and polyisocyanurates can be obtained by cyclotrimerization of polyisocyanates.
  • the conventionally operated cyclotrimerization proceeding from monomeric diisocyanates is - as described above - a strongly exothermic reaction. This has to date considerably restricted the possible applications and the trimerization levels that are still achievable in technical terms and in an efficient manner.
  • polyisocyanates this means monomeric and/or oligomeric polyisocyanates alike. For understanding of many aspects of the invention, however, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates.
  • oligomeric polyisocyanates this means polyisocyanates formed from at least two monomeric diisocyanate molecules, i.e. compounds that constitute or contain a reaction product formed from at least two monomeric diisocyanate molecules.
  • oligomeric polyisocyanates from monomeric diisocyanates is also referred to here as modification of monomeric diisocyanates.
  • modification means the reaction of monomeric diisocyanates to give oligomeric polyisocyanates having, for example, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • hexamethylene diisocyanate is a "monomeric diisocyanate” since it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:
  • oligomeric polyisocyanates within the context of the invention.
  • Representatives of such "oligomeric polyisocyanates" are, proceeding from monomeric HDI, for example, HDI isocyanurate and HDI biuret, each of which are formed from three monomeric HDI units:
  • Oligomeric polyisocyanates are known to those skilled in the art and are described, for example, in the literature below. Oligomeric polyisocyanates are also commercially available as important precursors and intermediates, especially as hardener components, for polyurethane lacquers and adhesives.
  • Polyisocyanate composition A) in the context of the invention refers to the isocyanate component in the initial reaction mixture. In other words, this is the sum total of all compounds in the initial reaction mixture that have isocyanate groups.
  • the polyisocyanate composition A) is thus used as reactant in the process according to the invention.
  • polyisocyanate composition A) especially to “providing the polyisocyanate composition A)"
  • the polyisocyanate composition A) used as reactant in the trimerization is low in monomers (i.e. low in monomeric diisocyanates) and already contains oligomeric polyisocyanates.
  • the polyisocyanate composition A) consists entirely or to an extent of 80%, 85%, 90%, 95%, 98%, 99% or 99.5% by weight, based in each case on the weight of the polyisocyanate composition A), of oligomeric polyisocyanates.
  • oligomeric polyisocyanates is based on the polyisocyanate composition A), meaning that they are not formed, for instance, as intermediate during the process according to the invention, but are already present in the polyisocyanate composition A) used as reactant on commencement of the reaction.
  • the polyisocyanate composition A) has a proportion of monomeric diisocyanates in the polyisocyanate composition A) of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the polyisocyanate composition A).
  • a proportion of monomeric diisocyanates in the polyisocyanate composition A) of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the polyisocyanate composition A).
  • the crosslinking reaction stops before all the free isocyanate groups have been consumed it may be the case that the crosslinking reaction stops before all the free isocyanate groups have been consumed.
  • the polyisocyanate composition A) has a content of monomeric diisocyanates of not more than 5% by weight, especially not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the polyisocyanate composition A).
  • a content of monomeric diisocyanates of not more than 5% by weight, especially not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the polyisocyanate composition A).
  • Essentially free means here that the content of monomeric diisocyanates is not more than 0.5% by weight, based on the weight of the polyisocyanate composition A).
  • the polyisocyanate composition A) used is low in monomers. In practice, this can especially be achieved by using, as polyisocyanate composition A), oligomeric polyisocyanates, in the preparation of which the actual modification reaction has been followed in each case by at least one further process step for removal of the unconverted excess monomeric diisocyanates.
  • This removal of monomers can be effected in a particularly practical manner by processes known per se, preferably by thin-film distillation under high vacuum or by extraction with suitable solvents that are inert toward isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • suitable solvents that are inert toward isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • the polyisocyanate composition A) according to the invention is obtained by modifying monomeric diisocyanates with subsequent removal of unconverted monomers.
  • the polyisocyanate composition A) may comprise an extra monomeric diisocyanate.
  • extra monomeric diisocyanate means that it is a monomeric diisocyanate different from the monomeric diisocyanates which have been used for preparation of the oligomeric polyisocyanates present in the polyisocyanate composition A). Addition of extra monomeric diisocyanate may be advantageous for achievement of specific technical effects, for example a particular hardness.
  • the polyisocyanate composition A) has a proportion of extra monomeric diisocyanate in the polyisocyanate composition A) of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the polyisocyanate composition A).
  • the polyisocyanate composition A) has a content of extra monomeric diisocyanate of not more than 5% by weight, especially not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the polyisocyanate composition A).
  • the total content of monomeric diisocyanate in the polyisocyanate composition A) should always be not more than 20% by weight, as described above.
  • the polyisocyanate composition A) may contain monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two, i.e. having more than two isocyanate groups per molecule.
  • monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two has been found to be advantageous in order to influence the network density of the polyisocyanurate plastic.
  • the polyisocyanate composition A) has a proportion of monomeric monoisocyanates and/or monomeric isocyanates having an isocyanate functionality greater than two in the polyisocyanate composition A) of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the polyisocyanate composition A).
  • the polyisocyanate composition A) has a content of monomeric monoisocyanates and/or monomeric isocyanates having an isocyanate functionality greater than two of not more than 5% by weight, especially not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the polyisocyanate composition A).
  • no monomeric monoisocyanate or monomeric isocyanate having an isocyanate functionality greater than two is used in the trimerization reaction according to the invention.
  • the low-monomer polyisocyanate composition A) and the oligomeric polyisocyanates present therein are typically obtained by modifying simple aliphatic, cycloaliphatic, araliphatic and/or aromatic monomeric diisocyanates or mixtures of such monomeric diisocyanates.
  • the oligomeric polyisocyanates may, in accordance with the invention, especially have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • the oligomeric polyisocyanates have at least one of the following oligomeric structure types or mixtures thereof:
  • oligomeric polyisocyanates that are a mixture of at least two oligomeric polyisocyanates, the at least two oligomeric polyisocyanates differing in terms of structure.
  • This structure is preferably selected from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure, and mixtures thereof.
  • trimerization reactions with oligomeric polyisocyanates of just one defined structure starting mixtures of this kind can lead to an effect on the Tg value, which is advantageous for many applications.
  • a polyisocyanate composition A) consisting of at least one oligomeric polyisocyanate having biuret, allophanate, isocyanurate and/or iminooxadiazinedione structure and mixtures thereof.
  • the polyisocyanate composition A) is one containing only a single defined oligomeric structure, for example exclusively or for the most part isocyanurate structure. In general, as a result of the preparation, however, several different oligomeric structures are always present alongside one another in the polyisocyanate composition A).
  • a polyisocyanate composition A) is regarded as a polyisocyanate composition of a single defined oligomeric structure when an oligomeric structure selected from uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure is present to an extent of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, especially preferably 80 mol% and particularly 90 mol%, based in each case on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the polyisocyanate composition A).
  • the oligomeric polyisocyanates are those which have mainly an isocyanurate structure and which may contain the abovementioned uretdione, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure only as by-products.
  • one embodiment of the invention envisages the use of a polymer composition A) of a single defined oligomeric structure, the oligomeric structure being an isocyanurate structure and being present to an extent of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, especially preferably 80 mol% and particularly 90 mol%, based in each case on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the polyisocyanate composition A).
  • oligomeric polyisocyanates having very substantially no isocyanurate structure, and containing mainly at least one of the abovementioned uretdione, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure types.
  • the polyisocyanate composition A) consists to an extent of 50 mol%, preferably 60 mol%, more preferably 70 mol%, especially preferably 80 mol% and particularly 90 mol%, based in each case on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the polyisocyanate composition A), of oligomeric polyisocyanates having a structure type selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • a further embodiment of the invention envisages the use of a low-isocyanurate polyisocyanate composition A) having, based on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the polyisocyanate composition A), less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol% and especially preferably less than 20 mol%, 10 mol% or 5 mol% of isocyanurate structures.
  • a further embodiment of the invention envisages the use of a polymer composition A) of a single defined oligomeric structure type, said oligomeric structure type being selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure and this structure type being present to an extent of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, especially preferably 80 mol% and particularly 90 mol%, based on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the polyisocyanate composition A).
  • the proportions of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure in the polyisocyanate composition A) can be determined, for example, by NMR spectroscopy.
  • NMR spectroscopy Preferably, it is possible here to use 13 C NMR spectroscopy, preferably in proton-decoupled form, since the oligomeric structures mentioned give characteristic signals.
  • the oligomeric polyisocyanate composition A) for use in the process according to the invention and/or the oligomeric polyisocyanates present therein preferably have a (mean) NCO functionality of 2.0 to 5.0, preferably of 2.3 to 4.5.
  • results of particular practical relevance are established when the polyisocyanate composition A) to be used in accordance with the invention has a content of isocyanate groups of 8.0% to 28.0% by weight. It has been found to be of particular practical relevance when the polyisocyanate composition A) according to the invention has a content of isocyanate groups of 14.0% to 25.0% by weight, based in each case on the weight of the polyisocyanate composition A).
  • the polyisocyanate composition A) according to the invention is defined in that it contains oligomeric polyisocyanates which have been obtained from monomeric diisocyanates, irrespective of the nature of the modification reaction used, with observation of an oligomerization level of 5% to 45%, preferably 10% to 40%, more preferably 15% to 30%.
  • Oligomerization level is understood here to mean the percentage of isocyanate groups originally present in the starting mixture which are consumed during the preparation process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures.
  • Suitable polyisocyanates for production of the polyisocyanate composition A) for use in the process according to the invention and the oligomeric polyisocyanates present therein are any desired polyisocyanates obtainable in various ways, for example by phosgenation in the liquid or gas phase or by a phosgene-free route, for example by thermal urethane cleavage. Particularly good results are established when the polyisocyanates are monomeric diisocyanates.
  • Preferred monomeric diisocyanates are those having a molecular weight in the range from 140 to 400 g/mol, having aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups, for example 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,
  • Suitable monomeric monoisocyanates which can optionally be used in the polyisocyanate composition A) are, for example, n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, 3- or 4-methylcyclohexyl isocyanate or any desired mixtures of such monoisocyanates.
  • An example of a monomeric isocyanate having an isocyanate functionality greater than two which can optionally be added to the polyisocyanate composition A) is 4-isocyanatomethyloctane 1,8-diisocyanate (triisocyanatononane; TIN).
  • the polyisocyanate composition A) contains not more than 30% by weight, especially not more than 20% by weight, not more than 15% by weight, not more than 10% by weight, not more than 5% by weight or not more than 1% by weight, based in each case on the weight of the polyisocyanate composition A), of aromatic polyisocyanates.
  • aromatic polyisocyanate means a polyisocyanate having at least one aromatically bonded isocyanate group.
  • a polyisocyanate composition A) having exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups is used.
  • Aliphatically and cycloaliphatically bonded isocyanate groups are respectively understood to mean isocyanate groups bonded to an aliphatic and cycloaliphatic hydrocarbyl radical.
  • a polyisocyanate composition A) consisting of or comprising one or more oligomeric polyisocyanates is used, where the one or more oligomeric polyisocyanates has/have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups.
  • the polyisocyanate composition A) consists to an extent of at least 70%, 80%, 85%, 90%, 95%, 98% or 99% by weight, based in each case on the weight of the polyisocyanate composition A), of polyisocyanates having exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups. Practical experiments have shown that particularly good results can be achieved with polyisocyanate compositions A) in which the oligomeric polyisocyanates present therein have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups.
  • a polyisocyanate composition A) which consists of or comprises one or more oligomeric polyisocyanates, where the one or more oligomeric polyisocyanates is/are based on 1,5-diisocyanatopentane, (PDI), 1,6-diisocyanatohexane (HDI), isophorone diisocyanate (IPDI) or 4,4'-diisocyanatodicyclohexylmethane or mixtures thereof.
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • IPDI isophorone diisocyanate
  • 4,4'-diisocyanatodicyclohexylmethane or mixtures thereof 4,4'-diisocyanatodicyclohexylmethane or mixtures thereof.
  • the polyisocyanurates according to the invention are obtainable by catalytic trimerization by the process according to the invention.
  • Catalytic means in the presence of at least one tertiary organic phosphine catalyst B).
  • a tertiary organic phosphine catalyst is a catalyst containing or consisting of at least one tertiary organic phosphine.
  • a tertiary organic phosphine is especially understood to mean a compound having a trivalent phosphorus to which organic substituents are bonded.
  • Organic substituents are understood to mean especially alkyl groups, cycloalkyl groups, aralkyl groups or aryl groups, where the aryl groups may optionally be substituted.
  • alkyl groups are understood to mean those groups that have up to 10 and preferably 2 to 8 carbon atoms and are linear or branched.
  • this definition includes, for example, the meanings of methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl.
  • cycloalkyl group is understood to mean a cyclic saturated group having up to 10 and preferably 3 to 8 carbon atoms.
  • Cycloalkyl groups of this kind are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl.
  • Aralkyl groups refer in accordance with the invention to aryl-substituted alkyl groups having up to 12 and preferably 7 to 10 carbon atoms.
  • Aralkyl groups of this kind are, for example, benzyl, phenethyl, 2- and 3-phenylpropyl, 2-benzylpropyl, 1- and 2-naphthylethyl.
  • an aryl group is understood to mean a mono- or bicyclic unsaturated group having cyclically delocalized electrons and having 6 to 10 and preferably 6 carbon atoms.
  • Examples of an aryl group are phenyl, naphthyl.
  • the aryl group may be alkyl-substituted, i.e. substituted by an alkyl group having up to 10 and preferably having 1 to 6 carbon atoms.
  • optional alkyl group substituents of this kind for the aryl group are methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl.
  • a heterocyclic ring as used here is understood to mean a ring having 4 to 6 ring members, such as cyclobutane, cyclopentane or cyclohexane, in which one carbon atom has been replaced by the phosphorus atom of the tertiary organic phosphine catalyst.
  • Suitable tertiary organic phosphine catalysts B) for the process according to the invention are in principle all tertiary organic phosphines which accelerate the trimerization of isocyanate groups to isocyanurate structures. Since isocyanurate formation, depending on the catalyst used, is frequently accompanied by side reactions, for example dimerization to give uretdione structures or trimerization to form iminooxadiazinediones (called asymmetric trimers), and by allophanatization reactions in the case of presence of urethane groups in the starting polyisocyanate, the term "trimerization" shall also synonymously represent these reactions that proceed additionally in the context of the present invention.
  • trimerization means that predominantly cyclotrimerizations of at least 50%, preferably at least 60%, more preferably at least 70% and especially at least 80% of isocyanate groups present in the polyisocyanate composition A) to give isocyanurate structural units are catalysed.
  • side reactions especially those to give uretdione, allophanate and/or iminooxadiazinedione structures, typically occur and can even be used in a controlled manner in order to advantageously affect, for example, the Tg of the polyisocyanurate plastic obtained.
  • tertiary organic phosphine catalysts B) of the general formula (I) are used in which
  • Suitable tertiary organic phosphine catalysts B) are, for example, tertiary phosphines having linear aliphatic substituents, such as trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tripropylphosphine, dibutylethylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-tert-butylphosphine, pentyldimethylphosphine, pentyldiethylphosphine, pentyldipropylphosphine, pentyldibutylphosphine, pentyldihexylphosphine, dipentylmethylphosphine, dipentylethylphosphine, dipentylpropylphosphine, dipentylbutylphosphine, dipentylhexylpho
  • tertiary organic phosphine catalysts B) that are suitable for the process according to the invention are, for example, also the tertiary phosphines known from EP 1 422 223 A1 that have at least one cycloaliphatic radical bonded directly to phosphorus, for example cyclopentyldimethylphosphine, cyclopentyldiethylphosphine, cyclopentyldi-n-propylphosphine, cyclopentyldiisopropylphosphine, cyclopentyldibutylphosphine with any isomeric butyl radicals, cyclopentyldihexylphosphine with any isomeric hexyl radicals, cyclopentyldioctylphosphine with any isomeric octyl radicals, dicyclopentylmethylphosphine, dicyclopentylethylphosphine, di
  • tertiary organic phosphine catalysts B) for the process according to the invention are, for example, also the tertiary phosphines that are known from EP 1 982 979 A1 and have one or two tertiary alkyl radicals bonded directly to phosphorus, for example tert-butyldimethylphosphine, tert-butyldiethylphosphine, tert-butyldi-n-propylphosphine, tert-butyldiisopropylphosphine, tert-butyldibutylphosphines with any isomeric butyl radicals for the non-tertiary butyl radicals, tert-butyldihexylphosphines with any isomeric hexyl radicals, but where not more than one of the hexyl radicals has a tertiary carbon atom bonded directly to phosphorus,
  • the tertiary organic phosphine catalyst B is selected from the group of the tertiary phosphines with linear aliphatic substituents mentioned.
  • Very particularly preferred tertiary organic phosphine catalysts B) are tri-n-butylphosphine and/or trioctylphosphine.
  • the tertiary organic phosphine catalyst B) is generally used in a concentration based on the weight of the polyisocyanate composition A) used of 0.0005% to 5.0% by weight, preferably of 0.0010% to 3.0% by weight and more preferably of 0.0015% to 2.0% by weight.
  • the tertiary organic phosphine catalysts B) that are used in the process according to the invention generally have sufficient solubility in the polyisocyanate composition A) in the amounts that are required for initiation of the oligomerization reaction.
  • the catalyst B) is therefore preferably added to the polyisocyanate composition A) in neat form.
  • the tertiary organic phosphine catalysts B) can also be used dissolved in a suitable organic solvent to improve their incorporability.
  • the dilution level of the catalyst solutions can be chosen freely within a very wide range. Catalyst solutions of this kind are typically catalytically active over and above a concentration of about 0.01% by weight.
  • Suitable catalyst solvents are, for example, solvents that are inert toward isocyanate groups, for example hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or monoethyl ether acetate, diethylene glycol ethyl and butyl ether acetate, propylene glycol monomethyl ether acetate, 1-methoxy-2-propyl acetate, 3-methoxy-n-butyl acetate, propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactones, such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone and ⁇ -methylcaprolactone, but also solvents such as N-methyl
  • catalyst solvents which bear groups reactive toward isocyanates and can be incorporated into the polyisocyanurate resin.
  • solvents are mono- or polyhydric simple alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, ethylene glycol, propylene glycol, the isomeric butanediols, 2-ethylhexane-1,3-diol or glycerol; ether alcohols, for example 1-methoxy-2-propanol, 3-ethyl-3-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol
  • the polyisocyanurate plastics obtainable by the process according to the invention feature very good light stability. Nevertheless, it is optionally possible to use standard auxiliaries and additives C) as well in the production thereof, for example standard fillers C w ), UV stabilizers C x ), antioxidants C y ), mould release agents C z ), water scavengers, slip additives, defoamers, levelling agents, rheology additives, flame retardants and/or pigments.
  • auxiliaries and additives C are typically present in the polyisocyanurate plastic in an amount of less than 10% by weight, preferably less than 5% by weight, more preferably up to 3% by weight, based on the polyisocyanate composition A).
  • Flame retardants are typically present in the polyisocyanurate plastic in amounts of not more than 70% by weight, preferably not more than 50% by weight and more preferably not more than 30% by weight, calculated as the total amount of flame retardants used, based on the total weight of the polyisocyanate composition A).
  • Suitable fillers C w are, for example, glass fibres, carbon fibres, ceramic fibres, nylon fibres, aramid fibres, but also AlOH 3 , CaCO 3 , metal pigments such as TiO 2 and further known standard fillers. These fillers C w ) are preferably used in amounts of not more than 70% by weight, preferably not more than 50% by weight, more preferably not more than 30% by weight, calculated as the total amount of fillers used, based on the total weight of the polyisocyanate composition A).
  • Suitable UV stabilizers C x may preferably be selected from the group consisting of piperidine derivatives, for example 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-1,2,2,6,6-pentamethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-1-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) suberate, bis(2,2,6,6-tetramethyl-4-piperidyl) dodecanedioate; benzophenone derivatives, for example 2,4-dihydroxy-, 2-hydroxy-4-methoxy-, 2-hydroxy-4-octoxy-, 2-hydroxy-4-dodecyloxy- or 2,2'-dihydroxy-4-dodecyloxybenzophenone; benzotriazole derivatives, for example 2-(2H-benzotri
  • Particularly preferred UV stabilizers C x ) for the polyisocyanurate plastics producible in accordance with the invention are those which fully absorb radiation of wavelength ⁇ 400 nm. These include, for example, the benzotriazole derivatives mentioned. Very particularly preferred UV stabilizers are 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol and/or 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)phenol.
  • UV stabilizers C x mentioned by way of example to the polyisocyanate composition A), preferably in amounts of 0.001% to 3.0% by weight, more preferably 0.01% to 2% by weight, calculated as the total amount of UV stabilizers used, based on the total weight of the polyisocyanate composition A).
  • Suitable antioxidants C y are preferably sterically hindered phenols, which may be selected preferably from the group consisting of 2,6-di-tert-butyl-4-methylphenol (ionol), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. If required, they can be used either individually or in any desired combinations with one another.
  • antioxidants C y are preferably used in amounts of 0.01% to 3.0% by weight, more preferably 0.02% to 2.0% by weight, calculated as the total weight of the amount of antioxidants used, based on the total weight of the polyisocyanate composition A).
  • the process according to the invention can, apart from the small amounts of any catalyst solvents to be used in addition, be conducted in a solvent-free manner.
  • the polyisocyanate component can optionally also be diluted with organic solvents to reduce the processing viscosity.
  • Solvents suitable for the purpose are, for example, the catalyst solvents inert toward isocyanate groups that have already been described above.
  • auxiliaries and additives C) added may also be internal mould release agents C z ).
  • nonionic surfactants that contain perfluoroalkyl or polysiloxane units and are known as mould release agents, quaternary alkyl ammonium salts, for example trimethylethylammonium chloride, trimethylstearylammonium chloride, dimethylethylcetylammonium chloride, triethyldodecylammonium chloride, trioctylmethylammonium chloride and diethylcyclohexyldodecylammonium chloride, acidic mono- and dialkyl phosphates having 2 to 18 carbon atoms in the alkyl radical, for example ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, octyl phosphate, dioctyl phosphate, isodecyl phosphate, diisodec
  • Particularly preferred mould release agents C z are the acidic mono- and dialkyl phosphates mentioned, most preferably those having 8 to 12 carbon atoms in the alkyl radical.
  • Internal mould release agents C z are used in the process according to the invention, if appropriate, preferably in amounts of 0.01% to 3.0% by weight, more preferably 0.02% to 2.0% by weight, calculated as the total weight of the internal mould release agents used, based on the total weight of the polyisocyanate composition A).
  • the polyisocyanate composition A) described optionally but not necessarily under inert gas, for example nitrogen, and optionally with additional use of the aforementioned solvents and auxiliaries and additives C), a tertiary organic phosphine catalyst B) or a mixture of different tertiary organic phosphine catalysts B) of this kind is added and is mixed in homogeneously with the aid of a suitable mixing unit.
  • inert gas for example nitrogen
  • tertiary organic phosphine catalyst B) and of any solvent for additional use and of auxiliaries and additives C) takes place in any sequence, successively or in a mixture, in the above-specified amounts, generally at a temperature of 0 to 100°C, preferably of 15 to 80°C, more preferably of 20 to 60°C.
  • the mixture does not contain any catalyst that accelerates the reaction of isocyanate groups with water in a catalytically active amount. It is especially preferable that the mixture does not contain any tin compounds, for example tin(II) octoate or dibutyltin dilaurate.
  • the catalysed reaction mixtures thus obtained can be applied by different methods that are known per se.
  • a mixture of tertiary organic phosphine catalyst B) and polyisocyanate composition A) can be applied, for example, by spraying, painting, dipping, flow-coating, or with the aid of brushes, rollers or coating bars, in one or more layers, directly to any substrates, for example metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textiles, leather and paper, and these can optionally also be provided with standard primers prior to the coating.
  • the mixture of tertiary organic phosphine catalyst B) and polyisocyanate composition A) can be introduced into open or closed moulds, for example, by simple manual pouring, or with the aid of suitable machinery, for example the low-pressure or high-pressure machinery which is standard in polyurethane technology.
  • the phosphine-catalysed trimerization reaction generally already sets in at low temperatures and proceeds very homogeneously without apparent exothermicity.
  • the trimerization can optionally be accelerated, where the optimal reaction temperature, depending on the catalyst selected in each case, is from -20 to 200°C, preferably from 10 to 160°C, more preferably from 20 to 130°C.
  • the reaction temperature can be kept constant within the range specified over the entire curing process to give the polyisocyanurate, or else can be heated, for example, in a linear or stepwise manner up to a temperature greater than 80°C, preferably greater than 100°C, for example up to 130°C, over several hours or days.
  • the hardening is effected at room temperature, "room temperature” being understood to mean the temperature range between 0°C and 80°C and more preferably between 0°C and 60°C.
  • the hardening could be effected at more than 100°C or more than 120°C. However, this can lead to products with significant yellowing (see Example 9). If this effect is to be avoided, it is preferable to conduct the hardening at room temperature until the reaction mixture is no longer tacky, and only thereafter to raise the temperature to the aforementioned values. As Example 5 shows, yellowing of the product is prevented in this way.
  • process step b), in a preferred embodiment of the present invention is effected at a relative air humidity that does not permit blister-free curing of the reaction mixture using tin catalysts, for example tin(II) octoate or dibutyltin dilaurate.
  • the trimerization is effected at a relative air humidity of at least 20%, more preferably at least 30%, even more preferably at least 40% and most preferably at least 50%.
  • the hardening is effected in the presence of liquid water. The hardening here is preferably effected at a temperature between 0°C and 80°C.
  • process step b) in a particularly preferred embodiment of the present invention, is conducted at a relative air humidity of at least 75% or in direct contact with liquid water.
  • the hardening here is preferably effected at a temperature between 0°C and 80°C.
  • the trimerization reaction is complete after a period of a few hours or only after a few days.
  • the progress of the reaction can initially still be monitored by titrimetric determination of the NCO content, but gelation and solidification of the reaction mixture sets in rapidly as the reaction progresses, which makes wet-chemical analysis methods impossible.
  • the further conversion of isocyanate groups can then be monitored only by spectroscopic methods, for example by IR spectroscopy with reference to the intensity of isocyanate band at about 2270 cm -1 .
  • the polyisocyanurate plastics obtainable by the process according to the invention are preferably polyisocyanurates with a high degree of conversion, i.e. those in which the trimerization reaction to give polyisocyanurate structures is very substantially complete.
  • a trimerization reaction to give polyisocyanurate structures can be regarded as "very substantially complete” in the context of the present invention when at least 80%, preferably at least 90%, more preferably at least 95%, of the free isocyanate groups originally present in the polyisocyanate composition A) have reacted.
  • the polyisocyanate plastic according to the invention there are preferably not more than 20%, not more than 10%, more preferably not more than 5%, of the isocyanate groups originally present in the polyisocyanate composition A) in the polyisocyanurate plastic according to the invention.
  • This can be achieved by continuing the catalytic trimerization in the process according to the invention at least up to a conversion level at which only, for example, not more than 20% of the isocyanate groups originally present in the polyisocyanate composition A) are present, such that a polyisocyanurate with high conversion is obtained.
  • the percentage of isocyanate groups still present can be determined by comparison of the content of isocyanate groups in % by weight in the original polyisocyanate composition A) with the content of isocyanate groups in % by weight in the reaction product, for example by the aforementioned comparison of the intensity of the isocyanate band at about 2270 cm -1 by means of IR spectroscopy.
  • the invention also relates to the polyisocyanurate plastics obtainable by the process according to the invention characterized by the use of reaction mixtures which are free of tin compounds. These differ from those from the prior art, inter alia, in that they are transparent, blister-free and yellowing-stable. According to the nature of the starting polyisocyanate used, they also optionally contain further oligomeric structures as well as isocyanurate structures and are notable for excellent thermal stabilities. It is a further characteristic of the polyisocyanurate plastics according to the invention that the tertiary organic phosphine catalyst B) used for production of the polyisocyanurate plastic remains in the polyisocyanurate plastic.
  • the process according to the invention enables synthesis, in a simple manner, through suitable selection of starting polyisocyanates of different oligomeric structures, of polyisocyanurate plastics having different properties, for example different hardness levels, mechanical properties or glass transition temperatures.
  • the low exothermicity of the reaction according to the invention also permits the problem-free production of solid mouldings of large volume.
  • the NCO contents were determined by titrimetry as per DIN EN ISO 11909.
  • the residual monomer contents were measured to DIN EN ISO 10283 by gas chromatography with an internal standard.
  • the contents (mol%) of the uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures present in the starting polyisocyanates were calculated from the integrals of proton-decoupled 13 C NMR spectra (recorded on a Bruker DPX-400 instrument) and are each based on the sum total of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures present.
  • the glass transition temperature Tg was determined by means of DSC (differential scanning calorimetry) with a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, Germany) at a heating rate of 20°C/min.
  • Shore hardnesses were measured to DIN 53505 with the aid of a Zwick 3100 Shore hardness tester (from Zwick, Germany).
  • IR spectra were recorded on a Spectrum Two FT-IR spectrometer equipped with an ATR unit, from Perkin Elmer, Inc.
  • the starting polyisocyanate A1) prepared was an HDI polyisocyanate containing isocyanurate groups, prepared in accordance with Example 11 of EP-A 330 966 .
  • the reaction was stopped at an NCO content of the crude mixture of 40% by adding dibutyl phosphate.
  • unconverted HDI was removed by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar.
  • NCO content 21.8%
  • NCO functionality 3.4 Monomeric HDI: 0.1% Viscosity (23°C): 3000 mPas Density (20°C): 1.17 g/cm 3
  • the starting polyisocyanate A2) used was an HDI polyisocyanate containing biuret groups, prepared in accordance with the process of EP-A 0 150 769 , by reaction of 8.2 mol of HDI with 1.0 mol of water in the presence of 0.05 mol of pivalic anhydride at a temperature of 125°C.
  • an NCO content 23.0%
  • NCO functionality 3.2
  • Monomeric HDI 0.4%
  • polyisocyanate composition A For use as polyisocyanate composition A), the starting polyisocyanate A3) prepared was an HDI polyisocyanate containing allophanate and isocyanurate groups, prepared according to Example 1 of EP-A 496 208 . NCO content: 19.8% NCO functionality: 2.5 Monomeric HDI: 0.3% Viscosity (23°C): 570 mPas
  • the starting polyisocyanate A4) prepared was an HDI polyisocyanate containing isocyanurate and iminooxadiazinedione groups, prepared in accordance with Example 4 of EP-A 0 962 455 , by trimerization of HDI using a 50% solution of tetrabutylphosphonium hydrogendifluoride in isopropanol/methanol (2:1) as catalyst. The reaction was stopped at an NCO content of the crude mixture of 43% by adding dibutyl phosphate. Subsequently, unconverted HDI was removed by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar. NCO content: 23.4% NCO functionality: 3.2 Monomeric HDI: 0.2% Viscosity (23°C): 700 mPas
  • Example 1 shows that the process according to the invention (Example 1) with catalysis with a tertiary organic phosphine catalyst in the presence of air humidity affords an entirely transparent, blister-free polyisocyanurate plastic, whereas the use of a tin catalyst known from the prior art (Example 2), and likewise the simultaneous use of a tertiary organic phosphine catalyst and a tin catalyst, under otherwise identical trimerization conditions, leads to a polyisocyanurate material which foams because of the carbon dioxide formed in the isocyanate/water reaction, which is the reason why a multitude of blisters occur in the polyisocyanurate plastic obtained.

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Claims (15)

  1. Procédé pour la production d'une matière plastique de polyisocyanurate, comprenant les étapes suivantes :
    a) mise à disposition d'une composition A) de polyisocyanate qui comprend des polyisocyanates oligomériques et une faible teneur en diisocyanates monomériques, « une faible teneur en diisocyanates monomériques » signifiant que la composition A) de polyisocyanate possède une teneur en diisocyanates monomériques non supérieure à 20 % en poids,
    b) trimérisation de manière catalytique de la composition A) de polyisocyanate à une température comprise entre 0 °C et 80 °C en utilisant au moins un catalyseur B) de type phosphine organique tertiaire de la formule générale (I)
    Figure imgb0008
     dans laquelle
    R1, R2 et R3 sont des radicaux identiques ou différents et sont chacun un groupe alkyle ou cycloalkyle possédant jusqu'à 10 atomes de carbone, préférablement un groupe alkyle possédant 2 à 8 atomes de carbone ou un groupe cycloalkyle possédant 3 à 8 atomes de carbone, un groupe alkyle possédant 7 à 10 et préférablement 7 atomes de carbone, ou un groupe aryle qui possède 6 à 10 et préférablement 6 atomes de carbone et éventuellement substitué par des radicaux alkyles possédant jusqu'à 10 et préférablement 1 à 6 atomes de carbone, à la condition que pas plus d'un parmi les radicaux ne soit un groupe aryle et au moins l'un parmi les radicaux soit un groupe alkyle ou cycloalkyle, ou dans laquelle
    R1 et R2 sont de nature aliphatique et, joints l'un à l'autre, conjointement avec l'atome de phosphore, forment un cycle hétérocyclique possédant 4 6 éléments de cycle, où R3 est un groupe alkyle possédant jusqu'à 4 atomes de carbone.
  2. Procédé selon la revendication 1, le catalyseur B) de type phosphine organique tertiaire étant choisi dans le groupe constitué par la triméthylphosphine, la triéthylphosphine, la tri-n-propylphosphine, la tripropylphosphine, la dibutyléthylphosphine, la tri-n-butylphosphine, la triisobutylphosphine, la tri-tert-butylphosphine, la pentyldiméthylphosphine, la pentyldiéthylphosphine, la pentyldipropylphosphine, la pentyldibutylphosphine, la pentyldihexylphosphine, la dipentylméthylphosphine, la dipentyléthylphosphine, la dipentylpropylphosphine, la dipentylbutylphosphine, la dipentylhexylphosphine, la dipentyloctylphosphine, la tripentylphosphine, l'hexyldiméthylphosphine, l'hexyldiéthylphosphine, l'hexyldipropylphosphine, l'hexyldibutylphosphine, la dihexylméthylphosphine, la dihexyléthylphosphine, la dihexylpropylphosphine, la dihexylbutylphosphine, la trihexylphosphine, la trioctylphosphine, la tribenzylphosphine, la benzyldiméthylphosphine, la diméthylphenylphosphine et le butylphosphacyclopentane et des mélanges de ceuxci.
  3. Procédé selon la revendication 1 ou 2, le catalyseur de type phosphine organique tertiaire étant la la tri-n-butylphosphine et/ou la trioctylphosphine.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la trimérisation catalytique et conduite au moins jusqu'à un taux de conversion auquel il y a seulement au plus 20 % des groupes isocyanate présents à l'origine dans la composition A) de polyisocyanate.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la composition A) de polyisocyanate est constituée jusqu'à une quantité d'au moins 80 %, 85 %, 90 %, 95 %, 98 %, 99 % ou 100 % en poids, sur la base en chaque cas du poids de la composition A) de polyisocyanate, de polyisocyanates possédant des groupes liés de manière exclusivement aliphatique et/ou cycloaliphatique.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que les polyisocyanates oligomériques comprennent un ou plusieurs polyisocyanates oligomériques qui sont composés ou constitués de 1,4-diisocyanatobutane, de 1,5-diisocyanatopentane, de 1,6-diisocyanatohexane, de diisocyanate d'isophorone ou de 4,4'-diisocyanatodicyclohexylméthane ou de mélanges correspondants.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la composition A) de polyisocyanate et/ou les polyisocyanates oligomériques possède une fonctionnalité moyenne de NCO de 2,0 à 5,0.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la composition A) de polyisocyanate possède une teneur en groupes isocyanate de 8,0 % à 28,0 % en poids, sur la base du poids de la composition A) de polyisocyanate.
  9. Procédé selon l'une des revendications 1 à 8, la composition A) de polyisocyanate possédant une teneur en diisocyanates monomériques non supérieure à 15 % en poids, non supérieure à 10 % en poids ou non supérieure à 5 % en poids, sur la base en chaque cas du poids de la composition A) de polyisocyanate.
  10. Procédé selon l'une des revendications 1 à 9, l'étape de procédé b) étant conduite à une humidité relative de l'air d'au moins 20 %.
  11. Procédé selon l'une des revendications 1 à 10, le mélange réactionnel ne contenant aucun catalyseur qui accélère la réaction de groupes isocyanate avec l'eau en une quantité catalytiquement active.
  12. Procédé selon l'une quelconque des revendications 1 à 11, le mélange réactionnel ne contenant aucun composé de l'étain.
  13. Matière plastique de polyisocyanurate pouvant être obtenu par le procédé selon la revendication 12.
  14. Revêtements, films, produits semi-finis ou moulages comprenant ou constitués d'une matière plastique de polyisocyanurate selon la revendication 13.
  15. Utilisation de la matière plastique de polyisocyanurate selon la revendication 13 pour la production de revêtements, de films, de produits semi-finis ou de moulages.
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CN109761903B (zh) * 2018-12-26 2020-07-28 万华化学集团股份有限公司 一种含有脲二酮基团的多异氰酸酯的制备方法
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CN109642015B (zh) 2022-09-23
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WO2018041800A1 (fr) 2018-03-08
US20190202963A1 (en) 2019-07-04
US11279790B2 (en) 2022-03-22
EP3507321A1 (fr) 2019-07-10

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